- Photoinduced hydrogen atom abstraction in N-(adamantyl)phthalimides: structure-reactivity study in the solid state
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Adamantyl-functionalized phthalimides were synthesized and the probability of intramolecular photochemical hydrogen atom abstraction in the solid state analyzed by X-ray crystallographic analyses. These analyses and solid-state photolyses showed that the parameters determining photochemical reactivity for typical carbonyl compounds in the solid state can also be extended to phthalimides. Only N-(2-adamantyl)phthalimide underwent a solid-state photochemical reaction, which is the first example in the phthalimide series. This reaction is regio- and stereoselective, resulting in an endo-alcohol. On the other hand, the photoreaction of N-(2-adamantyl)phthalimide in solution gives an exo-alcohol as the main product together with an endo-alcohol and a benzazepindione.
- Basari?, Nikola,Horvat, Margareta,Frankovi?, Oliver,Mlinari?-Majerski, Kata,Neud?rfl, J?rg,Griesbeck, Axel G.
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- A Facile Reduction of Azides to Amines Using Hydrazine
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A variety of alkyl and aryl azides were reduced in high yields to the corresponding amines by reaction with hydrazine in refluxing methanol in the presence of palladium.
- Malik, A. A.,Preston, S. B.,Archibald, T. G.,Cohen, M. P.,Baum, K.
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- New one-step synthesis of isonitriles
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A new one-step synthesis of isonitriles is described. The starting materials are a primary amine, chloroform, sodium hydride, and the phase-transfer catalyst 15-crown-5 ether, and the solvent is benzene. Five compounds are used to illustrate the features of the new synthesis: 1-adamantyl isocyanide (2a), 2-adamantyl isocyanide (2b), cis-1,8- diisocyano-p-menthane (2c), 2,4,6-trimethylphenyl isocyanide (2d), and trityl isocyanide (2e). The present synthesis is superior to the existing published syntheses because of its yields are good, the by-products are innocuous (H2 gas and NaCl), and its workup is simple. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file. Copyright Taylor & Francis Group, LLC.
- Bardsley, Kathryn,Hagigeorgiou, Michael,Lengyel, Istvan,Cesare, Victor
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- General and selective synthesis of primary amines using Ni-based homogeneous catalysts
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The development of base metal catalysts for industrially relevant amination and hydrogenation reactions by applying abundant and atom economical reagents continues to be important for the cost-effective and sustainable synthesis of amines which represent highly essential chemicals. In particular, the synthesis of primary amines is of central importance because these compounds serve as key precursors and central intermediates to produce value-added fine and bulk chemicals as well as pharmaceuticals, agrochemicals and materials. Here we report a Ni-triphos complex as the first Ni-based homogeneous catalyst for both reductive amination of carbonyl compounds with ammonia and hydrogenation of nitroarenes to prepare all kinds of primary amines. Remarkably, this Ni-complex enabled the synthesis of functionalized and structurally diverse benzylic, heterocyclic and aliphatic linear and branched primary amines as well as aromatic primary amines starting from inexpensive and easily accessible carbonyl compounds (aldehydes and ketones) and nitroarenes using ammonia and molecular hydrogen. This Ni-catalyzed reductive amination methodology has been applied for the amination of more complex pharmaceuticals and steroid derivatives. Detailed DFT computations have been performed for the Ni-triphos based reductive amination reaction, and they revealed that the overall reaction has an inner-sphere mechanism with H2metathesis as the rate-determining step.
- Beller, Matthias,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Jiao, Haijun,Murugesan, Kathiravan,Wei, Zhihong
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p. 4332 - 4339
(2020/05/18)
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- The Synthesis of Primary Amines through Reductive Amination Employing an Iron Catalyst
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The reductive amination of ketones and aldehydes by ammonia is a highly attractive method for the synthesis of primary amines. The use of catalysts, especially reusable catalysts, based on earth-abundant metals is similarly appealing. Here, the iron-catalyzed synthesis of primary amines through reductive amination was realized. A broad scope and a very good tolerance of functional groups were observed. Ketones, including purely aliphatic ones, aryl–alkyl, dialkyl, and heterocyclic, as well as aldehydes could be converted smoothly into their corresponding primary amines. In addition, the amination of pharmaceuticals, bioactive compounds, and natural products was demonstrated. Many functional groups, such as hydroxy, methoxy, dioxol, sulfonyl, and boronate ester substituents, were tolerated. The catalyst is easy to handle, selective, and reusable and ammonia dissolved in water could be employed as the nitrogen source. The key is the use of a specific Fe complex for the catalyst synthesis and an N-doped SiC material as catalyst support.
- B?umler, Christoph,Bauer, Christof,Kempe, Rhett
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p. 3110 - 3114
(2020/06/01)
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- Cerium-Catalyzed C-H Functionalizations of Alkanes Utilizing Alcohols as Hydrogen Atom Transfer Agents
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Modern photoredox catalysis has traditionally relied upon metal-to-ligand charge-transfer (MLCT) excitation of metal polypyridyl complexes for the utilization of light energy for the activation of organic substrates. Here, we demonstrate the catalytic application of ligand-to-metal charge-transfer (LMCT) excitation of cerium alkoxide complexes for the facile activation of alkanes utilizing abundant and inexpensive cerium trichloride as the catalyst. As demonstrated by cerium-catalyzed C-H amination and the alkylation of hydrocarbons, this reaction manifold has enabled the facile use of abundant alcohols as practical and selective hydrogen atom transfer (HAT) agents via the direct access of energetically challenging alkoxy radicals. Furthermore, the LMCT excitation event has been investigated through a series of spectroscopic experiments, revealing a rapid bond homolysis process and an effective production of alkoxy radicals, collectively ruling out the LMCT/homolysis event as the rate-determining step of this C-H functionalization.
- An, Qing,Chen, Yuegang,Liu, Weimin,Pan, Hui,Wang, Xin,Wang, Ziyu,Zhang, Kaining,Zuo, Zhiwei
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supporting information
p. 6216 - 6226
(2020/04/27)
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- Potential Synthetic Adaptogens: V. Synthesis of Cage Monoamines by the Schwenk–Papa Reaction
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The reduction of cage ketoximes under Schwenk–Papa reaction conditions was studied to establish that the d,l, d- and l-camphor oximes are smoothly reduced to the corresponding amines in high yields. At the same time, d,l-norcamphor and adamantan-2-one oximes undergo partial catalytic deoximation to form a mixture of the corresponding amines and alcohols.
- Brunilin, R. V.,Mkrtchyan, A. S.,Nawrozkij, M. B.,Novakov, I. A.,Vernigora, A. A.,Voloboev, S. N.,Vostrikova, O. V.
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p. 1742 - 1748
(2020/01/11)
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- Reusable Nickel Nanoparticles-Catalyzed Reductive Amination for Selective Synthesis of Primary Amines
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The preparation of nickel nanoparticles as efficient reductive amination catalysts by pyrolysis of in situ generated Ni-tartaric acid complex on silica is presented. The resulting stable and reusable Ni-nanocatalyst enables the synthesis of functionalized and structurally diverse primary benzylic, heterocyclic and aliphatic amines starting from inexpensive and readily available carbonyl compounds and ammonia in presence of molecular hydrogen. Applying this Ni-based amination protocol, -NH2 moiety can be introduced in structurally complex compounds, for example, steroid derivatives and pharmaceuticals.
- Murugesan, Kathiravan,Beller, Matthias,Jagadeesh, Rajenahally V.
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supporting information
p. 5064 - 5068
(2019/03/19)
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- Binding and Proton Blockage by Amantadine Variants of the Influenza M2WT and M2S31N Explained
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While aminoadamantanes are well-established inhibitors of the influenza A M2 proton channel, the mechanisms by which they are rendered ineffective against M2S31N are unclear. Solid state NMR, isothermal titration calorimetry, electrophysiology,
- Tzitzoglaki, Christina,Wright, Anna,Freudenberger, Kathrin,Hoffmann, Anja,Tietjen, Ian,Stylianakis, Ioannis,Kolarov, Felix,Fedida, David,Schmidtke, Michaela,Gauglitz, Günter,Cross, Timothy A.,Kolocouris, Antonios
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supporting information
p. 1716 - 1733
(2017/03/17)
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- MOF-derived cobalt nanoparticles catalyze a general synthesis of amines
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The development of base metal catalysts for the synthesis of pharmaceutically relevant compounds remains an important goal of chemical research. Here, we report that cobalt nanoparticles encapsulated by a graphitic shell are broadly effective reductive amination catalysts. Their convenient and practical preparation entailed template assembly of cobaltdiamine- dicarboxylic acid metal organic frameworks on carbon and subsequent pyrolysis under inert atmosphere.The resulting stable and reusable catalysts were active for synthesis of primary, secondary, tertiary, and N-methylamines (more than 140 examples).The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, or nitro compounds, and molecular hydrogen under industrially viable and scalable conditions, offering cost-effective access to numerous amines, amino acid derivatives, and more complex drug targets.
- Jagadeesh, Rajenahally V.,Murugesan, Kathiravan,Alshammari, Ahmad S.,Neumann, Helfried,Pohl, Marga-Martina,Radnik, J?rg,Beller, Matthias
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p. 326 - 332
(2017/09/28)
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- 2-Substituted and 2,2-disubstituted adamantane derivatives as models for studying substituent chemical shifts and C-Hax?Yax cyclohexane contacts - results from experimental and theoretical NMR spectroscopic chemical shifts and DFT structures
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Abstract The complete 1H and 13C NMR chemical shifts assignment for various 2-substituted and 2,2-disubstituted adamantane derivatives 1-38 in CDCl3 solution was realized on the basis of NMR experiments combined with chemical structure information and DFT-GIAO (B3LYP/6-31+G(d,p)-GIAO) calculations of chemical shifts in solution. Substituent-induced 13C NMR chemical shifts (SCS) are discussed. C-Hax?Yax contacts are a textbook prototype of steric hindrance in organic chemistry. The nature of these contacts will be further investigated in this work on basis of new adamantane derivatives, which are substituted at C-2 to provide models for 1,4-C-Hax?Yax and 1,5-C-Hax?Yax contacts. The B3LYP/6-31+G(d,p) calculations predicted the presence of NBO hyperconjugative attractive interactions between C-Hax and Yax groups along C-Hax?Yax contacts. The 1H NMR signal separation, Δδ(γ-CH2), reflects the strength of the H-bonded C-Haxa?Yax contact.
- Kolocouris, Antonios,Koch, Andreas,Kleinpeter, Erich,Stylianakis, Ioannis
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supporting information
p. 2463 - 2481
(2015/03/30)
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- Selective synthesis of primary amines by reductive amination of ketones with ammonia over supported Pt catalysts
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Supported platinum catalysts are studied for the reductive amination of ketones under ammonia and hydrogen. For a model reaction with 2-adamantanone, Pt-loaded MoOx/TiO2 (Pt-MoOx/TiO2) shows the highest yield of primary amine. The catalyst is effective for the selective transformation of various aliphatic and aromatic ketones to the corresponding primary amines, which demonstrates the first example of the selective synthesis of primary amines by this reaction. The yield of the amine increases with increase in the negative shift of the C£O stretching band in the infrared spectra of adsorbed acetone on the catalysts, suggesting that Lewis acid sites on the support material play an important role in this catalytic system.
- Nakamura, Yoichi,Kon, Kenichi,Touchy, Abeda Sultana,Shimizu, Ken-Ichi,Ueda, Wataru
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p. 921 - 924
(2015/03/18)
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- N-alkylation of ammonia and amines with alcohols catalyzed by Ni-loaded CaSiO3
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Nickel nanoparticles loaded onto calcium silicate (Ni/CaSiO3) have been prepared by ion-exchange method followed by in situ H 2-reduction of the calcined precursor. Ni/CaSiO3 was found to be effective for the catalytic direct synthesis of primary amines from alcohols and NH3 under relatively mild conditions. Various aliphatic alcohols are tolerated, and the turnover number (TON) was higher than those of Ru-based homogeneous catalysts. The catalyst was recoverable and was reused. Effects of the surface oxidation states and particle size of Ni on the catalytic activity were studied by infrared (IR) investigation of the states of adsorbed CO and transmission electron microscopy (TEM). It is clarified that the surface Ni0 sites on small (3 nm) sized Ni nanoparticles are the catalytically active species. Ni/CaSiO3 was also effective for the alkylation of anilines and aliphatic amines with various alcohols (benzyl and aliphatic alcohols) under additive free conditions; primary amines were converted into secondary amines and secondary amines into tertiary amines.
- Shimizu, Ken-Ichi,Kanno, Shota,Kon, Kenichi,Hakim Siddiki,Tanaka, Hideyuki,Sakata, Yoshihisa
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p. 134 - 138
(2014/06/09)
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- Heterogeneous Ni catalyst for direct synthesis of primary amines from alcohols and ammonia
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This paper reports the synthesis of primary amines from alcohols and NH3 by an Al2O3-supported Ni nanoparticle catalyst as the first example of heterogeneous and noble-metal-free catalytic system for this reaction without additional hydrogen sources under relatively mild conditions. Various aliphatic alcohols are tolerated, and turnover numbers were higher than those of Ru-based homogeneous catalysts. The catalyst was recoverable and was reused. The effects of the Ni oxidation states and the acid-base nature of support oxides on the catalytic activity are studied. It is clarified that the surface metallic Ni sites are the catalytically active species, and the copresence of acidic and basic sites on the support surface is also indispensable for this catalytic system.
- Shimizu, Ken-Ichi,Kon, Kenichi,Onodera, Wataru,Yamazaki, Hiroshi,Kondo, Junko N.
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p. 112 - 117
(2013/03/29)
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- PROCESS FOR THE DIRECT AMINATION OF ALCOHOLS USING AMMONIA TO FORM PRIMARY AMINES BY MEANS OF A XANTPHOS CATALYST SYSTEM
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The present invention relates to a chemocatalytic liquid-phase process for the direct one-stage amination of alcohols to primary amines by means of ammonia in high yields using a catalyst system containing at least one transition metal compound and a xantphos ligand.
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Paragraph 0063
(2014/01/08)
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- Improved ruthenium-catalyzed amination of alcohols with ammonia: Synthesis of diamines and amino esters
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Diamination of diols: The first homogeneously catalyzed diaminations of primary and secondary diols with ammonia give the corresponding diamines. Other primary as well as secondary alcohols including hydroxy-substituted esters can also be efficiently converted to primary amines. This atom-efficient and selective amination method proceeds in an ammonia atmosphere without additional hydrogen sources. Copyright
- Imm, Sebastian,Baehn, Sebastian,Zhang, Min,Neubert, Lorenz,Neumann, Helfried,Klasovsky, Florian,Pfeffer, Jan,Haas, Thomas,Beller, Matthias
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supporting information; experimental part
p. 7599 - 7603
(2011/10/01)
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- An efficient and general synthesis of primary amines by ruthenium-catalyzed amination of secondary alcohols with ammonia
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Atom efficiency and selectivity are the key features of the first homogeneously catalyzed amination of secondary alcohols with ammonia to give the corresponding primary amines (see scheme). This novel amination method relies on the commercially available catalyst [Ru3(CO)12]/ cataCXium PCy and does not require any additional source of hydrogen.
- Imm, Sebastian,Neubert, Lorenz,Neumann, Helfried,Beller, Matthias
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supporting information; experimental part
p. 8126 - 8129
(2011/02/22)
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- NOVEL PROCESS FOR PREPARING CARBOXY-CONTAINING PYRAZOLEAMIDO COMPOUNDS 597
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A process for preparing pharmaceutically acceptable compounds of formula (I) wherein R1, R2, R3, X, A and Y are as defined in the specification is described and claimed, together with processes for preparing some key inter
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(2010/08/09)
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- Copper-nitrene complexes in catalytic C-H amination
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(Chemical Equation Presented) Hydrocarbons activate! Isolable β-diketiminato dicopper-nitrene complexes such as 1 derived from the reaction of [{(Cl2NN)Cu}2(μ-benzene)] and 1-adamantylazide are potent towards nitrene insertion into unactivated sp 3-hybridized C-H bonds. 1 allows stoichiometric and catalytic intermolecular C-H amination of hydrocarbons to give secondary amines (see scheme). Catalyst loadings as low as 0.05 mol% may be used.
- Badiei, Yosra M.,Dinescu, Adriana,Dai, Xuliang,Palomino, Robert M.,Heinemann, Frank W.,Cundari, Thomas R.,Warren, Timothy H.
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supporting information; experimental part
p. 9961 - 9964
(2009/05/07)
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- PYRAZOLE DERIVATIVES AS 11-BETA-HSD1 INHIBITORS
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A compound of formula (I): and pharmaceutically -acceptable salts thereof wherein the variable groups are defined within; their use in the inhibition of 11βHSD1, processes for making them and pharmaceutical compositions comprising them are also described.
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Page/Page column 116
(2008/12/08)
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- Detection of biomolecules by sensitizer-linked substrates
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Methods and compositions for detecting and characterizing target biomolecules using sensitizer-linked substrate molecules are disclosed. High throughput screening assays and therapeutic applications of the inventions are also included.
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- Methods and compositions for treating amyloid-related diseases
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Methods, compounds, pharmaceutical compositions and kits are described for treating or preventing amyloid-related disease.
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Page/Page column 142; 146
(2010/11/24)
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- Chemoselective reductive alkylation of ammonia with carbonyl compounds: Synthesis of primary and symmetrical secondary amines
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An efficient, general procedure for highly chemoselective reductive mono-alkylation of ammonia with ketones is reported. Treatment of ketones with ammonia in ethanol and titanium(IV) isopropoxide, followed by in situ sodium borohydride reduction, and a straightforward workup afforded primary amines in good to excellent yields. Reductive alkylation of ammonia with aldehydes, on the other hand, afforded the corresponding symmetrical secondary amines selectively.
- Miriyala, Bruhaspathy,Bhattacharyya, Sukanta,Williamson, John S.
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p. 1463 - 1471
(2007/10/03)
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- METHODS AND COMPOSITIONS FOR TREATING AMYLOID-RELATED DISEASES
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Methods, compounds, pharmaceutical compositions and kits are described for treating or preventing amyloid-related disease.
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- Selective monoalkylation of ammonia: A high throughput synthesis of primary amines
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Primary amines are obtained in good to excellent yields by highly selective monoalkylation of ammonia with alkyl and aryl ketones using titanium(IV) isopropoxide and sodium borohydride.
- Bhattacharyya, Sukanta,Neidigh, Kurt A.,Avery, Mitchell A.,Williamson, John S.
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p. 1781 - 1783
(2007/10/03)
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- Salts of dihalo-3,4-dihydro-3-oxo-2-quinoxaline carboxylic acids and hindered amines
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Salts of 6,7-dihalo-3,4-dihydro-3-oxo-2-quinoxaline carboxylic acids and hindered amines, useful in combating influenza A and B.
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- Adamantyl containing guanidines
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Novel compounds of FIG. 1, pharmaceutical compositions thereof, and systemic means of administration for anti-arrhythmic and diuretic uses are disclosed: STR1
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